CN112981456A - Preparation method of Cu @ MIL-101-Cr electrocatalyst for efficiently preparing acetone - Google Patents
Preparation method of Cu @ MIL-101-Cr electrocatalyst for efficiently preparing acetone Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title abstract description 27
- 239000010411 electrocatalyst Substances 0.000 title abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 17
- 239000004917 carbon fiber Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims description 125
- 239000006185 dispersion Substances 0.000 claims description 44
- 239000010949 copper Substances 0.000 claims description 39
- 235000019441 ethanol Nutrition 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 34
- 239000002159 nanocrystal Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 21
- 239000012279 sodium borohydride Substances 0.000 claims description 21
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 21
- 239000005457 ice water Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
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- 238000007605 air drying Methods 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 6
- 235000019253 formic acid Nutrition 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 4
- 239000011736 potassium bicarbonate Substances 0.000 abstract description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 abstract description 3
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- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 abstract 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004098 selected area electron diffraction Methods 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 acetone Chemical compound 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
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- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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Abstract
一种高效制备丙酮的Cu@MIL‑101‑Cr电催化剂的制备方法，属于催化剂电极制取技术领域。发明利用具有高稳定性、对CO2具有高吸附选择性、含有微‑介孔多级孔道结构的经典MOFs—MIL‑101‑Cr为载体，采用浸渍法制备高活性位点Cu@MIL‑101‑Cr复合催化剂。将Cu@MIL‑101‑Cr与导电炭黑混合，利用涂布法将其负载到碳纤维上，得到Cu@MIL‑101‑Cr/C修饰的碳纤维电极。发现其在CO2饱和的0.1 M KHCO3水溶液中，显现出对液相产物甲醇、乙醇、丙酮和甲酸高电催化选择性，尤其是丙酮，其法拉第效率高达18.9%。
A preparation method of a Cu@MIL-101-Cr electrocatalyst for efficiently preparing acetone belongs to the technical field of catalyst electrode preparation. The invention uses the classical MOFs—MIL-101-Cr, which has high stability, high adsorption selectivity to CO 2 and contains micro-mesoporous hierarchical pore structure, as the carrier, and adopts the impregnation method to prepare high-active site Cu@MIL-101 ‑Cr composite catalyst. The Cu@MIL-101-Cr and conductive carbon black were mixed and loaded onto carbon fibers by coating method to obtain Cu@MIL-101-Cr/C modified carbon fiber electrodes. It was found to exhibit high electrocatalytic selectivity for liquid-phase products methanol, ethanol, acetone, and formic acid, especially acetone, with a Faradaic efficiency as high as 18.9% in CO2 -saturated 0.1 M KHCO3 aqueous solution.
Description
Technical Field
The invention belongs to the technical field of catalyst electrode preparation, and particularly relates to a preparation method of a Cu @ MIL-101-Cr electrocatalyst for efficiently preparing acetone.
Background
Introducing CO2Conversion to energy-intensive fuels and chemical feedstocks is an attractive solution to environmental protection and energy-regeneration sustainable development strategies. Electrochemically converting CO into CO with high efficiency and low energy consumption2Reduction to valuable small molecule energy is the preferred choice. The method can not only remove excessive CO2The conversion is carried out, and meanwhile, conversion products such as energy micromolecules such as formic acid, methanol, ethanol and the like can be stored and utilized, so that the dependence of human on fossil fuel can be effectively reduced. Thus, electrocatalytic reduction of CO2Is more and more favored by various scholars.
The metallic copper electrode is the only electrode material which is recognized at present and has higher hydrocarbon yield efficiency and reaction rate, and has the advantages of low cost, abundant reserves and the like. However, the disadvantage is that the overpotential is high, close to 1.0V. Electrocatalytic reduction of CO on copper foil electrodes in aqueous inorganic salt solution2The product is mainly formic acid (RHE) under lower negative potential (-0.6 to-1.0V vs. RHE)<25%)、CO(<20 percent) under higher negative potential (-1.0 to-1.2V vs. RHE), methane (<41%), ethylene (C)<23%), ethanol (1)<10%) with a significant Faraday efficiency (David N. Abram, Etoha R. Cave, Thomas F. Jaramillo, et al, New energies into the electrochemical reduction of carbon dioxide on metallic reactors [ J]. Energy & environmental science,2012,5(5):7050–7059)。
However, the surface of the copper foil electrode is dense, which can block CO2Contact and reaction with the electrodes are not favorable for diffusion of gas products. Obviously, modification and modification of the catalyst material is a key approach to improve selectivity and current density. The size effect of the nano material can not only increase the specific surface area of the nano material, but also provide abundant active sites for electrocatalytic reaction, thereby realizing the improvement of the reaction kinetics of the nano material. Nanoams, nanoparticles and copper nanoparticlesOxides have become a hotspot of research in this field. Studies have shown that the selectivity of the product strongly depends on the morphology, size and surface atomic configuration of the Cu electrode. The coordination numbers and chemisorption energies of atoms on the surface, corners, edges and lattice planes of metal nanoparticles differ, so that the catalytic activity of nanoparticles (Cu NPs) can be controlled in principle by controlling their size and surface structure (like pellet, chemistry Hemma, behafarred, et al, Particle size efficiencies in the catalytic electrochemical reduction of CO)2 on Cu nanoparticles[J]Journal of the American Chemical Society, 2014, 136(19): 6978-6786). At present, such regulation is mainly achieved by liquid phase synthesis with the aid of organic amines. However, as the particle size of the nanoparticles is reduced, the surface effect is enhanced, and the agglomeration phenomenon is aggravated, thereby affecting the catalytic activity and stability of the nanoparticles. In order to solve the problem, the introduced activating agent, stabilizing agent, coating agent and the like also increase the steric hindrance of the catalyst and prevent the adsorption of reactants on the surface of the catalyst, thereby limiting the catalytic activity of the catalyst to a certain extent.
Confining Cu NPs within a porous support can solve this problem. The metal organic framework Materials (MOFs) are a framework structure formed by mutually connecting metal base nodes (metal ions or metal ion clusters) and organic bridging molecules through coordination bonds, and have the characteristics of small crystal density, high porosity, uniform and adjustable pore diameter, large specific surface area and the like, such as classical MOFs-MIL-101-Cr. It can provide various limited space (2.9 and 3.4 nm cavities) for the growth of the Cu NPs so as to prevent the Cu NPs from agglomerating, and the regular ordered hierarchical pores are favorable for the high dispersion of the Cu NPs on the surfaces or in the pore canals and are favorable for reaction molecules (such as CO)2) Mass transfer and diffusion. By using it to CO2High adsorption selectivity of molecules and can also increase CO2Thereby effectively increasing CO2The efficiency of the electroreduction. Up to now, Cu NPs supported by original ecological MOFs and electrocatalytic reduction of CO thereof2The studies have not been reported.
Among various Cu-based electrocatalysts, the report that acetone is the main product is very rare (Kun Zoha, Xiaowa Nie, Haozhi Wang, et al. Selective electrochemical reaction of CO2 to an acetic one by single compressor atoms and N-bonded porous carbon [ J ]. Nature Communications, 2020, 11(1): 5791-5797).
Disclosure of Invention
The invention aims to provide a preparation method of a Cu @ MIL-101-Cr catalyst, which is simple and feasible, short in reaction period, high in material utilization rate, small in dosage, low in cost and good in stability.
The invention comprises the following steps:
1) preparing MIL-101-Cr nanocrystals: mixing and dissolving terephthalic acid, chromium nitrate nonahydrate and aqueous solution of sodium acetate, sealing, keeping the temperature constant, cooling to room temperature, filtering, washing a filter cake with deionized water, drying, purifying, performing suction filtration, and drying to obtain the MIL-101-Cr nanocrystal containing the micro-mesoporous hierarchical pore structure;
2）Cu2+preparation of @ MIL-101-Cr material: ultrasonically dispersing copper nitrate in DMF to obtain copper salt dispersion liquid, slowly adding the MIL-101-Cr nano crystal into the copper salt dispersion liquid under continuous stirring to obtain MIL-101-Cr and Cu2+The solid-liquid mixture of (1) is obtained by impregnating the pore canal with Cu2+Washing and centrifuging the MIL-101-Cr nanocrystal solid phase substance to obtain uniformly dispersed Cu2+@ MIL-101-Cr material;
3）Cu2+@MIL-101-Cr+preparation of ethanol dispersion: the Cu is added2+Ultrasonically dispersing the material of @ MIL-101-Cr in absolute ethyl alcohol, and stirring in an ice-water bath to obtain Cu2+@MIL-101-Cr+An ethanol dispersion;
4）NaBH4 +preparation of ethanol dispersion: reacting NaBH4Dispersing in absolute ethyl alcohol, stirring in ice-water bath to form NaBH4 +An ethanol dispersion;
5) preparation of Cu @ MIL-101-Cr catalyst: reacting the NaBH4 +Dropwise adding an ethanol dispersion to the Cu2+And continuing stirring in the @ MIL-101-Cr + ethanol dispersion liquid in an ice-water bath, centrifugally separating a solid-phase product, washing and drying to obtain the Cu @ MIL-101-Cr catalyst.
The inventionTo have high stability to CO2MIL-101-Cr with high adsorption selectivity and a micro-mesoporous hierarchical pore structure is used as a carrier, and a high-activity-site Cu @ MIL-101-Cr catalyst is prepared by adopting an impregnation method. The Cu @ MIL-101-Cr catalyst prepared by the method keeps the octahedral morphology of MIL-101-Cr, and the size of the carrier is uniform. The Cu NPs have good dispersibility, are uniformly loaded on the surface of the MIL-101-Cr and in the pore channels of the MIL-101-Cr, and have the particle size of 7 +/-1 nm. The invention uses an impregnation method to impregnate active components on an MIL-101-Cr carrier in the form of salt solution in the absence of stabilizers such as surfactants and the like, and the active components are impregnated on the inner surface of the MIL-101-Cr carrier, and the high dispersion catalyst is obtained after simple reduction and activation. The method is simple and easy to implement, short in reaction period, high in material utilization rate, small in dosage and low in cost, and the obtained catalyst material has good stability.
In addition, in the step 1), the MIL-101-Cr nanocrystals are in an octahedral shape, and the specific surface area is 3200-3400 m2·g-1. The MIL-101-Cr nanocrystal has high stability and CO resistance2Has high adsorption selectivity and contains micro-mesoporous multilevel pore canals.
In the step 2), the dispersion ratio of the copper nitrate to the DMF is 0.06-0.14 mmol: 20 ml. The dispersion ratio can make copper nitrate completely dissolved in DMF, and copper salt dispersion liquid with uniform dispersion is obtained after ultrasonic treatment.
In the step 2), the mixing ratio of the MIL-101-Cr nanocrystals to the copper salt dispersion liquid is 100 mg to 20 ml. The proportion can ensure that the copper particles are uniformly distributed on the surface of the MIL-101-Cr and in the pore canal, and the appearance is uniform.
In the step 2) and the step 5), the rotating speed of the centrifugation is 7000-9000 r/min, and the time is 5-10 min. Under the centrifugal rotation speed and the centrifugal rotation time, Cu NPs with uniform particle size (7 +/-1 nm) and uniform dispersion can be obtained.
In the step 3), the Cu2+The mixing ratio of the @ MIL-101-Cr nanocrystals to the absolute ethyl alcohol was 100 mg: 10 ml. The mixing ratio is such that Cu2+The @ MIL-101-Cr nanocrystals were dispersed in a relatively stable anhydrous ethanol solution.
In the step 4)The NaBH4The mixing ratio of the ethanol to the absolute ethyl alcohol is 7.5 mg: 1 ml. NaBH4The copper-based catalyst is stable in an absolute ethyl alcohol (ice-water bath) solution, the copper salt can be fully reduced by the proportion, and the morphology of MOFs is not damaged.
In the step 5), the NaBH4 +Anhydrous alcohol dispersion and said Cu2+@MIL-101-Cr+The volume ratio of the ethanol dispersion liquid is 1:5, and the dropping speed is 0.1-0.3 ml/min. Under the conditions of the mixture ratio and the dropping speed, the obtained Cu @ MIL-101-Cr is uniform in appearance and particle size and good in stability.
A preparation method of a Cu @ MIL-101-Cr/C electrode material comprises the steps of putting the Cu @ MIL-101-Cr catalyst, conductive carbon black and a Nafion film solution into absolute ethyl alcohol, conducting ultrasonic dispersion uniformly, continuing stirring at room temperature, then dropwise coating the surface of carbon fibers, and air-drying to obtain the Cu @ MIL-101-Cr/C electrode material.
The Cu @ MIL-101-Cr catalyst prepared by the method is loaded on carbon fibers, and is used as a working electrode for electrocatalytic reduction of CO2Adopts an H-shaped reactor, and is carried out at normal temperature and normal pressure in CO2Saturated 0.1M KHCO3In aqueous solution, the electrode material shows high electrocatalytic selectivity to liquid-phase products of methanol, ethanol, acetone and formic acid, particularly acetone, the Faraday efficiency is up to 18.9 percent, and CO is reduced in electrocatalysis2Preparation C2、C3The product field shows remarkable application prospect.
In addition, the mass ratio of the Cu @ MIL-101-Cr catalyst to the conductive carbon black is 1:2, the dropping amount is 160 mu L, and the loading area is 1 multiplied by 1 cm2. Cu @ MIL-101-Cr molecules are low in self conductivity, the catalytic performance of the Cu @ MIL-101-Cr material can be improved by doping the Cu @ MIL-101-Cr material with conductive carbon black with high conductivity, and under the condition, the electrode is applied to CO2The best reduction performance is achieved.
Drawings
FIG. 1 is a TEM photograph of MIL-101-Cr nanocrystals prepared in example 1 of the present invention, with a scale of 100 nm.
FIG. 2 is a TEM photograph of the Cu @ MIL-101-Cr catalyst prepared in example 1 of the present invention, with a scale of 100 nm.
FIG. 3 is a TEM photograph of the Cu @ MIL-101-Cr catalyst prepared in example 2 of the present invention, with a scale of 100 nm.
FIG. 4 is a TEM photograph of the Cu @ MIL-101-Cr catalyst prepared in example 3 of the present invention, with a scale of 100 nm.
FIG. 5 is an SEM picture of a Cu @ MIL-101-Cr catalyst prepared in example 3 of the present invention.
FIG. 6 is a HRTEM image of Cu @ MIL-101-Cr catalyst prepared in example 3 of the present invention, with a scale of 50 nm.
FIG. 7 is a particle size distribution plot of the Cu @ MIL-101-Cr catalyst prepared in example 3 of the present invention.
FIG. 8 is a plot of Selected Area Electron Diffraction (SAED) for the Cu @ MIL-101-Cr catalyst prepared in example 3 of the present invention, plotted at 5 nm.
FIG. 9 is a HRTEM image of Cu @ MIL-101-Cr catalyst prepared in example 3 of the present invention, with a scale of 5 nm.
FIG. 10 is an X-ray diffraction (XRD) pattern of MIL-101-Cr of the present invention and Cu @ MIL-101-Cr catalyst prepared in example 3.
FIG. 11 is a graph of nitrogen desorption curves and pore size distribution for the MIL-101-Cr catalyst of the present invention and the Cu @ MIL-101-Cr catalyst prepared in example 3.
FIG. 12 is a graph of MIL-101-Cr of the present invention and Cu @ MIL-101-Cr/C electrode prepared in example 3 in CO2Cyclic voltammograms in the atmosphere.
FIG. 13 is a current-time plot at different potentials for a Cu @ MIL-101-Cr/C electrode prepared in example 3 of the present invention.
FIG. 14 is a graph of the faradaic efficiency of the electrolysis product of the Cu @ MIL-101-Cr/C electrode prepared in example 3 of the present invention.
FIG. 15 is a FID test peak of the Cu @ MIL-101-Cr/C electrode electrolysis product prepared in example 3 of the present invention.
Detailed Description
In order to make the technical features, objects and advantages of the present invention more intuitive, embodiments of the present invention will be described in detail with reference to the following specific embodiments. The following examples are carried out in accordance with the invention and the scope of protection of the invention is not limited to the examples described below.
Example 1
Weighing 1.96g of terephthalic acid, 4.8g of chromium nitrate nonahydrate and 0.24g of sodium acetate, adding 60ml of distilled water, mixing and dissolving, placing in a stainless steel autoclave lined with polytetrafluoroethylene, sealing, keeping the temperature constant at 200 ℃ for 12 h, cooling to room temperature, filtering, washing and drying a filter cake with deionized water, soaking and purifying with 30mmol/L ammonium fluoride aqueous solution, performing suction filtration, and placing in a vacuum drying oven for drying at constant temperature of 150 ℃ to obtain the MIL-101-Cr nanocrystal containing the micro-mesoporous hierarchical pore structure.
Selecting the materials with uniform appearance, size of 200-500 nm and specific surface area of 3200-3400 m2·g-1Taking the MIL-101-Cr nanocrystal as a carrier, weighing 100 mg of the MIL-101-Cr nanocrystal, adding the MIL-101-Cr nanocrystal into a DMF (20 ml) solution containing 120.8 mg of copper nitrate, performing ultrasonic dispersion uniformly, and continuously stirring for 24 hours at room temperature; taking the pore canal and soaking with Cu2+Washing the MIL-101-Cr nanocrystal solid phase substance with DMF and ethanol for several times, and centrifuging to obtain Cu2+@ MIL-101-Cr material, ultrasonically dispersing the material in 10 ml of absolute ethyl alcohol, and uniformly stirring in ice-water bath to obtain Cu2+@MIL-101-Cr+And (3) ethanol dispersion.
Taking NaBH4Dispersing 15.0mg in 2 ml of absolute ethyl alcohol, and stirring uniformly in ice-water bath to form NaBH4 +Ethanol dispersion of NaBH4 +Dripping the ethanol dispersion liquid to Cu at the speed of 0.1-0.3 ml/min2+And continuing stirring for 2 h in an ethanol dispersion of @ MIL-101-Cr in an ice-water bath, centrifugally separating a solid-phase product, washing the solid-phase product for a plurality of times by using ethanol, and drying the product at 70 ℃ to obtain the Cu @ MIL-101-Cr catalyst.
Characterization of the Cu @ MIL-101-Cr catalyst: the Cu content of the prepared product is analyzed by adopting an Optima 7300 DV inductively coupled plasma spectrometer of Perkinelmer company in America, and the result shows that: the Cu content of the product prepared in example 1 was 4.5 wt%.
Preparing an electrode material: placing the Cu @ MIL-101-Cr catalyst and conductive carbon black in an absolute ethyl alcohol solution of a 0.5% Nafion membrane according to the mass ratio of 1:2, and performing ultrasonic uniform separationStirring for 2 hours at room temperature; dropping the dispersed solution on the surface of carbon fiber, air drying, and determining the coverage area of each time to be (1 × 1 cm)2) Air-drying to obtain carbon fiber loaded Cu @ MIL-101-Cr through electro-catalytic reduction of CO2Cathode material (Cu @ MIL-101-Cr/CD electrode material).
Example 2
Weighing 100 mg of MIL-101-Cr nanocrystals which are the same as in example 1, adding the MIL-101-Cr nanocrystals into a DMF (20 ml) solution containing 25.0 mg of copper nitrate, ultrasonically dispersing the mixture uniformly, and continuously stirring the mixture at room temperature for 24 hours; taking the pore canal and soaking with Cu2+Washing the MIL-101-Cr nanocrystal solid phase substance with DMF and ethanol for several times, and centrifuging to obtain Cu2+@ MIL-101-Cr material, ultrasonically dispersing the material in 10 ml of absolute ethyl alcohol, and uniformly stirring in ice-water bath to obtain Cu2+@MIL-101-Cr+And (3) ethanol dispersion.
Taking NaBH4Dispersing 15.0mg in 2 ml of absolute ethyl alcohol, and stirring uniformly in ice-water bath to form NaBH4 +Ethanol dispersion of NaBH4 +Dripping the ethanol dispersion liquid to Cu at the speed of 0.1-0.3 ml/min2+And continuing stirring for 2 h in an ethanol dispersion of @ MIL-101-Cr in an ice-water bath, centrifugally separating a solid-phase product, washing the solid-phase product for a plurality of times by using ethanol, and drying the product at 70 ℃ to obtain the Cu @ MIL-101-Cr catalyst.
Characterization of the Cu @ MIL-101-Cr catalyst: the Cu content of the prepared product is analyzed by adopting an Optima 7300 DV inductively coupled plasma spectrometer of Perkinelmer company in America, and the result shows that: the Cu content of the product prepared in example 2 was 2.6 wt%.
Preparing an electrode material: placing the Cu @ MIL-101-Cr catalyst and conductive carbon black in an absolute ethyl alcohol solution of a 0.5% Nafion membrane according to the mass ratio of 1:2, performing ultrasonic uniform dispersion, and stirring for 2 hours at room temperature; dropping the dispersed solution on the surface of carbon fiber, air drying, and determining the coverage area of each time to be (1 × 1 cm)2) Air-drying to obtain carbon fiber loaded Cu @ MIL-101-Cr through electro-catalytic reduction of CO2Cathode material (Cu @ MIL-101-Cr/CD electrode material).
Example 3
The same MIL-101-Cr nanocrystals 100 as in example 1 were weighedmg, adding the mixture into a DMF (20 ml) solution containing 13.0mg of copper nitrate, uniformly dispersing by ultrasonic, and continuously stirring for 24 hours at room temperature; taking the pore canal and soaking with Cu2+Washing the MIL-101-Cr nanocrystal solid phase substance with DMF and ethanol for several times, and centrifuging to obtain Cu2+@ MIL-101-Cr material, ultrasonically dispersing the material in 10 ml of absolute ethyl alcohol, and uniformly stirring in ice-water bath to obtain Cu2+@MIL-101-Cr+And (3) ethanol dispersion.
Taking NaBH4Dispersing 13.0mg in 2 ml of absolute ethyl alcohol, and stirring uniformly in ice-water bath to form NaBH4 +Ethanol dispersion of NaBH4 +Dripping the ethanol dispersion liquid to Cu at the speed of 0.1-0.3 ml/min2+And continuing stirring for 2 h in an ethanol dispersion of @ MIL-101-Cr in an ice-water bath, centrifugally separating a solid-phase product, washing the solid-phase product for a plurality of times by using ethanol, and drying the product at 70 ℃ to obtain the Cu @ MIL-101-Cr catalyst.
Characterization of the Cu @ MIL-101-Cr catalyst: the Cu content of the prepared product is analyzed by adopting an Optima 7300 DV inductively coupled plasma spectrometer of Perkinelmer company in America, and the result shows that: the Cu content of the product prepared in example 3 was 1.8 wt%.
Preparing an electrode material: placing the Cu @ MIL-101-Cr catalyst and conductive carbon black in an absolute ethyl alcohol solution of a 0.5% Nafion membrane according to the mass ratio of 1:2, performing ultrasonic uniform dispersion, and stirring for 2 hours at room temperature; dropping the dispersed solution on the surface of carbon fiber, air drying, and determining the coverage area of each time to be (1 × 1 cm)2) Air-drying to obtain carbon fiber loaded Cu @ MIL-101-Cr through electro-catalytic reduction of CO2Cathode material (Cu @ MIL-101-Cr/CD electrode material).
Product Properties
As can be seen from fig. 1 to 6: the catalysts obtained in examples 1, 2 and 3 all maintain the octahedral structure of the MIL-101-Cr nanocrystals, and composite materials with different Cu NPs loading amounts can be observed, and the Cu NPs are reduced in size (all less than 10 nm) along with the reduction of the copper content, but are uniformly loaded on the surfaces of the MIL-101-Cr nanocrystals and in the channels of the MIL-101-Cr nanocrystals. In example 3, the Cu loading is 1.8wt%, the Cu NPs size is 6 +/-1 nm (figure 7), and a more obvious ring grain can be clearly seen from a Selected Area Electron Diffraction (SAED) figure 8, wherein the ring grain corresponds to the (111) crystal face and the (200) crystal face of Cu from inside to outside respectively. The lattice diffraction fringes of the Cu NPs can be clearly seen in the HRTEM image of FIG. 9, with the main lattice spacings of about 0.208 nm and 0.181 nm, corresponding to the (111) plane of Cu and the (200) plane of Cu, respectively.
By way of example, the characterization of the 1.8wt% Cu @ MIL-101-Cr catalyst of example 3 is selected and it can be seen from FIG. 10 that: NaBH4The main diffraction peak positions of the MIL-101-Cr are kept unchanged after reduction, which shows that the skeleton of the MOFs is still kept stable; no significant diffraction peaks were observed for copper and its oxides, indicating a lower copper loading or a smaller copper loading size; after impregnation, the MIL-101-Cr skeleton has a lower crystallinity, resulting in a larger peak width of the diffraction peak.
As can be seen from fig. 11: n of sample at 77K2The adsorption and desorption isotherms are shown as type I isotherms, which show the micropore structural characteristics of the material. In a pore size distribution curve, the pore state of the carrier MIL-101-Cr is obviously changed after Cu is loaded, and the pore state corresponds to N2The adsorption capacity decreases and the two main pore distributions shift to the left (low radius).
Electrocatalytic reduction of CO to materials2And (3) testing the performance:
an electrode (Cu @ MIL-101-Cr/C, cathode) prepared by supporting 1.8wt% of the Cu @ MIL-101-Cr catalyst of example 3 on carbon fiber was used as a working electrode, a platinum sheet as a counter electrode, an Ag/AgCl electrode as a reference electrode, and CO in an H-type electrolytic cell2Gas saturated 0.1M KHCO3Cyclic voltammetric and potentiostatic electrolysis tests were carried out for the electrolytes, and the products were qualitatively and quantitatively analyzed by means of gas chromatography and ion chromatography.
The cyclic voltammogram of the Cu @ MIL-101-Cr/C electrode and the cyclic voltammogram of the blank carbon fiber and the blank MIL-101-Cr carrier are shown in FIG. 12; the time-current curves of the Cu @ MIL-101-Cr/C electrode under different potentials (-0.7 to-1.5V vs. Ag/AgCl or-0.1 to-0.9V vs. RHE) are shown in FIG. 13; the Faraday efficiency profile of the liquid phase electrolysis product of the Cu @ MIL-101-Cr/C electrode is shown in FIG. 14.
As can be seen from fig. 12: the blank carbon fiber electrode is in a-1.5-1.0V vs. Ag/AgCl potential areaThe current density between the carbon fiber and the carbon fiber is very low, which indicates that the carbon fiber is opposite to CO in the potential interval2Almost has no catalytic action. MIL-101-Cr/C support and Cu @ MIL-101-Cr/C electrode pairs for CO versus a bare carbon fiber electrode2All have certain catalytic effect, and the Cu @ MIL-101-Cr/C catalyst shows the highest catalytic current.
As can be seen from fig. 13: the Cu @ MIL-101-Cr/C catalyst can achieve the stability of current in a short time within a wide potential range and lasts for 4 hours.
As can be seen from FIG. 14, the preparation of C by the Cu @ MIL-101-Cr/C electrode pair2，C3The product has obvious activity, the liquid phase product comprises methanol, ethanol, acetone and formic acid, and the gas phase main product is H2And trace amounts of CO. The application of electric potential has certain influence on the kind and selectivity of liquid phase product. In general, acetone and methanol are main products at low potential (-0.7 to-1.1V vs. Ag/AgCl), the products show volcanic distribution along with the increase of the potential, the acetone can reach up to 19.8 percent at-0.9V (vs. Ag/AgCl), and the methanol can reach up to 6.3 percent (-0.8V); ethanol at-1.1V can reach 11.8%; the faradaic efficiency of formic acid increases significantly above-1.0V, reaching a maximum of 18.0% at-1.4V.
Claims (10)
1. A preparation method of a Cu @ MIL-101-Cr catalyst is characterized by comprising the following steps:
1) preparing MIL-101-Cr nanocrystals: mixing and dissolving terephthalic acid, chromium nitrate nonahydrate and aqueous solution of sodium acetate, sealing, keeping the temperature constant, cooling to room temperature, filtering, washing a filter cake with deionized water, drying, purifying, performing suction filtration, and drying to obtain the MIL-101-Cr nanocrystal containing the micro-mesoporous hierarchical pore structure;
2）Cu2+preparation of @ MIL-101-Cr material: ultrasonically dispersing copper nitrate in DMF to obtain copper salt dispersion liquid, slowly adding the MIL-101-Cr nano crystal into the copper salt dispersion liquid under continuous stirring to obtain MIL-101-Cr and Cu2+The solid-liquid mixture of (1) is obtained by impregnating the pore canal with Cu2+Washing and centrifuging the MIL-101-Cr nanocrystal solid phase substance to obtain uniformly dispersed Cu2+@ MIL-101-Cr materialFeeding;
3）Cu2+@MIL-101-Cr+preparation of ethanol dispersion: the Cu is added2+Ultrasonically dispersing the material of @ MIL-101-Cr in absolute ethyl alcohol, and stirring in an ice-water bath to obtain Cu2+@MIL-101-Cr+An ethanol dispersion;
4）NaBH4 +preparation of ethanol dispersion: reacting NaBH4Dispersing in absolute ethyl alcohol, stirring in ice-water bath to form NaBH4 +An ethanol dispersion;
5) preparation of Cu @ MIL-101-Cr catalyst: reacting the NaBH4 +Dropwise adding an ethanol dispersion to the Cu2+And continuing stirring in the @ MIL-101-Cr + ethanol dispersion liquid in an ice-water bath, centrifugally separating a solid-phase product, washing and drying to obtain the Cu @ MIL-101-Cr catalyst.
2. The preparation method of claim 1, wherein in the step 1), the MIL-101-Cr nanocrystals are octahedral and have a specific surface area of 3200-3400 m2·g-1。
3. The method according to claim 1, wherein in the step 2), the dispersion ratio of the copper nitrate to the DMF is 0.06-0.14 mmol: 20 ml.
4. The method according to claim 1, wherein the mixing ratio of the MIL-101-Cr nanocrystals to the copper salt dispersion in step 2) is 100 mg: 20 ml.
5. The method according to claim 1, wherein in the step 2) and the step 5), the rotation speed of the centrifugation is 7000 to 9000 r/min, and the time is 5 to 10 min.
6. The method of claim 1, wherein the mixing ratio of the MIL-101-Cr nanocrystals to the absolute ethanol in the step 3) is 100 mg: 10 ml.
7. The method of claim 1, wherein in step 4), the NaBH is added4The mixing ratio of the ethanol to the absolute ethyl alcohol is 7.5 mg: 1 ml.
8. The method of claim 1, wherein in step 5), the NaBH is added4 +Anhydrous alcohol dispersion and said Cu2+The volume ratio of the @ MIL-101-Cr + ethanol dispersion liquid is 1:5, and the dropping speed is 0.1-0.3 ml/min.
9. A preparation method of a Cu @ MIL-101-Cr/C electrode material is characterized by taking the Cu @ MIL-101-Cr catalyst, conductive carbon black and Nafion film solution of claim 1, placing the solution in absolute ethyl alcohol, performing ultrasonic dispersion uniformly, continuing stirring at room temperature, then dropwise coating the solution on the surface of carbon fibers, and performing air drying to obtain the Cu @ MIL-101-Cr/C electrode material.
10. The production method according to claim 9, wherein the mass ratio of the Cu @ MIL-101-Cr catalyst to the conductive carbon black is 1:2, the dropping amount is 160 μ L, and the supported area is 1 x 1 cm2。
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